CN105164223B - Electroconductive adhesive sheet, its manufacturing method and use its electric terminal - Google Patents

Electroconductive adhesive sheet, its manufacturing method and use its electric terminal Download PDF

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Publication number
CN105164223B
CN105164223B CN201480021189.0A CN201480021189A CN105164223B CN 105164223 B CN105164223 B CN 105164223B CN 201480021189 A CN201480021189 A CN 201480021189A CN 105164223 B CN105164223 B CN 105164223B
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mentioned
adhesive sheet
electroconductive
conductive
base material
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CN105164223A (en
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山上晃
仓田吉博
高野博树
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/21—Paper; Textile fabrics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0862—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/26—Presence of textile or fabric
    • C09J2400/263—Presence of textile or fabric in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)

Abstract

The present invention relates to a kind of electroconductive adhesive sheets, the electroconductive adhesive sheet is characterized in that, it is the electroconductive adhesive sheet in the conductive adhesive phase of at least one side of conductive substrate, above-mentioned conductive substrate is the conductive substrate as obtained from including the plating of electroless plating to the implementation of wet type Polyester non-woven fabrics base material, whole compared with above-mentioned conductive adhesive oxidant layer, above-mentioned conductive adhesive oxidant layer contains electroconductive particle in the range of the mass % of 3 mass %~50.

Description

Electroconductive adhesive sheet, its manufacturing method and use its electric terminal
Technical field
The present invention relates to the conductive adhesives that can be used in such as manufacture of electronic equipments such as portable electronic piece terminal etc. Piece.
Background technology
In recent years, it is highly integrated constantly to push away with miniaturization, slimming and the high performance of the electronic equipments such as communication equipment Into.When manufacturing above-mentioned electronic equipment, with shielding can from electronic equipment generate electromagnetic wave, to any part assign antistatic property Deng for the purpose of, in most cases using electroconductive adhesive sheet.
As above-mentioned electroconductive adhesive sheet, such as known have on the conductive substrate formed by metal foil containing conduction The bonding sheet of the conductive adhesive oxidant layer of property filler is (referring for example to patent document 1 and 2.).
Anyway, it is as described above used metal foil electroconductive adhesive sheet be in terms of flexibility it is insufficient, Therefore adherend surface there are it is small differential when, can exist can not follow above-mentioned differential portion and in adherend and adhesive phase The interstitial situation in interface.
On the other hand, industrial circle requirement can be when above-mentioned electroconductive adhesive sheet is secured at the errors present of adherend Its horizontal re-workability being easily peeled off immediately after pasting.
But in most cases, electroconductive adhesive sheet as described above is insufficient in terms of above-mentioned re-workability, is deposited In the situation that can not be recycled and correctly paste.
There are no find the electric conductivity of the level as described above taken into account and can fully shield electromagnetic wave etc., can follow The horizontal flexibility in differential portion etc. possessed by adherend and the electroconductive adhesive sheet of re-workability.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-263030 publications
Patent document 2：Japanese Unexamined Patent Publication 2009-79127 publications
The content of the invention
Problems to be solved by the invention
Problem to be solved by this invention is, provides a kind of leading for level taken into account and can fully shield electromagnetic wave etc. Electrically, the horizontal flexibility in differential portion etc. possessed by adherend and the electroconductive adhesive sheet of re-workability can be followed.
The method used for solving the problem
In the present invention, the above subject is solved by using a kind of electroconductive adhesive sheet, at least the one of conductive substrate Among the electroconductive adhesive sheet of the conductive adhesive phase of mask, above-mentioned conductive substrate is to wet type Polyester non-woven fabrics base material Obtained from implementation includes the plating of electroless plating,
Whole compared with above-mentioned conductive adhesive oxidant layer, above-mentioned conductive adhesive oxidant layer contains the mass % of 3 mass %~50 Electroconductive particle.
Invention effect
The electroconductive adhesive sheet of the present invention, which can be taken into account, can fully shield the horizontal electric conductivity of electromagnetic wave etc., can chase after With possessed by adherend it is fine it is concave-convex wait caused by differential portion etc. horizontal flexibility and re-workability, have pair The excellent bonding force of adherend, it is thus possible to be suitably used for such as the electromagnetism that can be used in the manufacture electronic equipment Wave screen covers piece, ground connection fixation bonding sheet for preventing electrostatic etc..
Description of the drawings
Fig. 1 is the skeleton diagram for the configuration example for representing the electroconductive adhesive sheet of the present invention.
Fig. 2 is the skeleton diagram for the configuration example for representing the electroconductive adhesive sheet of the present invention.
Fig. 3 is the figure of the tracing ability evaluation result for the electroconductive adhesive sheet for representing embodiment 1.
Fig. 4 is the figure of the tracing ability evaluation result for the electroconductive adhesive sheet for representing reference example 1.
Specific embodiment
The electroconductive adhesive sheet of the present invention is characterized in that：In the conductive adhesive of at least one side of conductive substrate Among the electroconductive adhesive sheet of layer, above-mentioned conductive substrate is to include electroless plating to the implementation of wet type Polyester non-woven fabrics base material Obtained from the plating of processing；Whole compared with above-mentioned conductive adhesive oxidant layer, above-mentioned conductive adhesive oxidant layer contains 3 matter Measure the electroconductive particle of the mass % of %~50.
" piece " described in the present invention means that at least one side in conductive substrate has at least one layer of conductive adhesive The form of layer.In addition, sheet above includes all product forms such as sheet, web-like, lamellar, banding (tape shapes).
The composition of electroconductive adhesive sheet as the present invention, can enumerate for example has individual layer in the one side of conductive substrate Or the above-mentioned conductive adhesive oxidant layer of multilayer composition, be respectively provided on the two sides of above-mentioned conductive substrate that single-layer or multi-layer is above-mentioned to lead The composition of conductive adhesive layer.
As the electroconductive adhesive sheet of the present invention, can have above-mentioned conductive substrate and conductive adhesive as needed Other layers beyond layer.
As above-mentioned electroconductive adhesive sheet, it is preferable to use the bonding sheets of the overall thickness with less than 100 μm, more preferably use Bonding sheet with less than 60 μm of overall thickness is then able to maintain that excellent using the bonding sheet of the overall thickness with less than 40 μm Flexibility, electric conductivity and cementability and the slimming for contributing to electronic equipment etc., thus further preferably.
In addition, the lower limit of the overall thickness as above-mentioned electroconductive adhesive sheet, is preferably 5 μm or more.Wherein, above-mentioned overall thickness Refer to not include stripping film, the thickness of electroconductive adhesive sheet in itself.
As the conductive substrate for the electroconductive adhesive sheet for forming the present invention, can use by wet type Polyester nonwoven Cloth base material implementation includes base material obtained from the plating of electroless plating.
As above-mentioned conductive substrate, such as it is preferable to use the base material with 6 μm~50 μ m thicks, more preferable use has The base material of 10 μm~30 μ m thicks.
As above-mentioned conductive substrate, the tensile strength it is preferable to use its MD (flowing) direction is 3N/20mm~35N/ The base material of 20mm more preferably using the base material for 5N/20mm~30N/20mm, is further preferably used as 10N/20mm~27N/ The base material of 20mm.
In addition, as above-mentioned conductive substrate, it is preferable to use its TD (width) direction tensile strength for 0.5N/20mm~ The base material of 35N/20mm, more preferably using for 3N/20mm~30N/20mm base material, further preferably using for 10N/20mm~ The base material of 27N/20mm.
By using MD (flowing) directions with above range and the electric conductivity base of the tensile strength in TD (width) direction Material is difficult to the fragmentation for causing electroconductive adhesive sheet when reprocessing (stripping), excellent re-workability is able to maintain that, moreover, energy Enough obtain conductive base material and the electroconductive adhesive sheet of the good adaptation of conductive adhesive oxidant layer.
As above-mentioned conductive substrate, using its [tensile strength in the tensile strength in MD directions/TD directions] 0.7~ The base material of 1.3 scope is then difficult to the fragmentation for causing electroconductive adhesive sheet when reprocessing (stripping), be able to maintain that it is excellent again Processability, so it is preferred that.Wherein, above-mentioned tensile strength refers to according to JIS Z0237-2010 with the speed tensile of 300mm/min So as to the value measured.
In addition, as above-mentioned conductive substrate, it is preferable to use the sheet resistance values with 0.5 Ω/25mm × below 25mm The base material in (x-axis direction, y-axis direction), more preferably using sheet resistance value (the x-axis side with 0.1 Ω/25mm × below 25mm To y-axis direction) base material, further preferably using with 0.05 Ω/25mm × below 25mm sheet resistance value (x-axis side To y-axis direction) base material, assigned using the base material of the sheet resistance value (x, y) with 0.01 Ω/25mm × below 25mm It is particularly preferred in terms of superior electric conductivity.
In addition, as above-mentioned conductive substrate, it is preferable to use the vertical surface electricity with 0.1 Ω/25mm × below 25mm The base material of resistance value (z-axis direction), more preferably using vertical surface resistance value (the z-axis side with 0.05 Ω/25mm × below 25mm To) base material, it is preferable to use the base materials of the vertical surface resistance value (z-axis direction) with 0.03 Ω/25mm × below 25mm, make Base material with the vertical surface resistance value (z-axis direction) with 0.01 Ω/25mm × below 25mm is assigning superior conduction Property aspect be particularly preferred.Wherein, above-mentioned sheet resistance value (x-axis direction, y-axis direction) and vertical surface resistance value (z-axis side To) assay method refer to the value measured by method described in embodiment.
When manufacturing above-mentioned conductive substrate, wet type Polyester non-woven fabrics base material is used.By using above-mentioned specific nonwoven Cloth base material can prevent the peeling of the coating formed by plating, can obtain leading with superior re-workability Electrical bonding sheet.
As above-mentioned wet type Polyester non-woven fabrics base material, can use by being carried out to the polyester fiber being scattered in water etc. Material obtained from papermaking.
As above-mentioned polyester fiber, it is preferable to use the fiber for example with 2 μm~10 μm of diameter, more preferable use has The fiber of 3 μm~8 μm of diameter.
It is not particularly limited, can be enumerated for example using cylinder mould machine, short net paper machine, length as above-mentioned papermaking process Net paper machine, the method for tilting short net paper machine.
It as above-mentioned wet type Polyester non-woven fabrics base material, is preferably used in by after above method papermaking, for making polyester The purpose bonded between fiber and the base material heated etc..
As above-mentioned wet type Polyester non-woven fabrics base material, in terms of superior flexibility and intensity is taken into account, it is preferable to use With 2g/m2~20g/m2The base material of the weight per unit area of scope, more preferably using with 4g/m2~16g/m2The list of scope The base material of position area weight, using with 6g/m2~15g/m2The base material of the weight per unit area of scope is being obtained slim and added again It is further preferred in terms of the excellent electroconductive adhesive sheet of work.
As above-mentioned wet type non-woven polyester cloth base material, it is preferable to use with 5 μ~50 μ m thick base material, more preferably use Base material with 10 μm~30 μ m thicks, particularly preferably using the base material with 14 μm~20 μ m thicks.
As above-mentioned wet type Polyester non-woven fabrics base material, the tensile strength it is preferable to use its MD (flowing) direction is 2N/ The base material of 20mm~30N/20mm more preferably using the base material for 5N/20mm~28N/20mm, is further preferably used as 10N/ The base material of 20mm~25N/20mm.
In addition, as above-mentioned wet type Polyester non-woven fabrics base material, the tensile strength it is preferable to use its TD (width) direction is The base material of 0.3N/20mm~30N/20mm more preferably using the base material for 2N/20mm~27N/20mm, further preferably uses For the base material of 9N/20mm~25N/20mm.Wherein, above-mentioned tensile strength refers to according to JIS Z0237-2010 with 300mm/min Speed tensile so as to measure value.
Above-mentioned conductive substrate can be by including at electroless plating the implementation of above-mentioned wet type Polyester non-woven fabrics base material The plating of reason manufactures.Here, " plating for including electroless plating " refers to, carries out 1 time or repeatedly without electricity It solves the processing of plating, carry out 1 time after above-mentioned electroless plating or processing that repeatedly electrolytic coating is handled, Yi Ji Carry out 1 time or repeatedly electrolytic coating processing after carry out again 1 time or repeatedly electroless plating processing.In the present invention, preferably Further implement electroless plating or electrolytic coating processing after electroless plating is implemented, more preferably implementing without electricity Further implement electrolytic coating processing after solution plating.
As above-mentioned electroless plating facture, can enumerate for example by by above-mentioned wet type unsaturated polyester system non-woven fabrics Base material impregnates in the liquid containing catalyst such as palladiums, in the electroless plating covering liquid containing metal ion and reducing agent, so as to In the method that the surface of above-mentioned non-woven fabrics base material forms metal epithelium.
In addition, when carrying out above-mentioned electroless plating, in addition to above-mentioned operation, it may also pass through and above-mentioned wet type is gathered Process that ester system non-woven fabrics base material is washed, the process for making above-mentioned activation of catalyst, to wet type Polyester non-woven fabrics base material and The process that the base material of plated processing is washed or dried.
As the preferred method of above-mentioned electroless plating, following methods can be enumerated：To above-mentioned wet type Polyester Non-woven fabrics base material washed, wash after, catalyst is assigned to above-mentioned wet type Polyester non-woven fabrics base material and is washed, makes above-mentioned urge Agent is activated and washed, and wet type Polyester non-woven fabrics base material in electroless plating covering liquid is impregnated, is washed, dried.
As the metal ion contained by above-mentioned electroless plating covering liquid, can enumerate such as copper, nickel, silver, platinum, aluminium from Son is preferred in terms of superior electric conductivity and low cost is taken into account using at least one kind of ion in copper or nickel, uses copper Ion is preferred in terms of superior adaptation is assigned.
Compared with above-mentioned electroless plating covering liquid, above-mentioned metal ion preferably comprises 0.001 mole/1~0.2 mole/1.
Above-mentioned metal ion be preferably from copper sulphate, nickel sulfate, nickel chloride, palladium bichloride, silver chlorate, silver nitrate and they Mixture ion, using copper sulphate, nickel sulfate, nickel chloride in terms of superior electric conductivity and low cost is taken into account, exist It is preferred in terms of suitable copper or nickel ion.
It, can be with use example such as sodium hypophosphite, sodium borohydride, boron as the reducing agent contained in above-mentioned electroless plating covering liquid Hydrofining, Rochelle salt, dimethyamine borane, diethylamine borane, formalin, the hydrazine hydrate as hydrazine compound, hydrochloric acid Hydrazine, hydrazine sulfate, methyl hydrazine, 1,2- dimethylhydrazines, acethydrazide, phenylhydrazine etc. or quinhydrones etc., it is preferable to use sodium hypophosphite, formals Woods.
Compared with above-mentioned electroless plating covering liquid, above-mentioned reducing agent preferably comprises 0.001 mole/1~0.4 mole/1.
As above-mentioned electroless plating covering liquid, it can use and also contain complexing agent, pH adjusting agent in addition to mentioned component, delay The plating liquid as auxiliary element such as electuary, plating accelerating agent, stabilizer.
As above-mentioned complexing agent, acylate, sulfydryl such as sodium citrate, potassium citrate, Rochelle salt can be used Acetic acid (Thioglycolic acid), ammonia, triethanolamine, glycine, ethylenediamine, ethylene diammine diacetate, o-aminophenol, Pyridine etc., it is preferable to use sodium citrates.
Compared with above-mentioned electroless plating covering liquid, above-mentioned complexing agent preferably comprises 0.001 mole/1~4.0 mole/1.
As above-mentioned pH adjusting agent, it is preferable to use such as sodium hydroxide, ammonium hydroxide, inorganic acid, organic acids etc..
As above-mentioned buffer, it is preferable to use such as alkali metal salt of organic acid, inorganic acid, sodium citrate, sodium acetate, chlorine Change ammonium, ammonium sulfate, hydroxycarboxylic acid, dihydric phosphate, boric acid, carbonic acid etc..
As above-mentioned plating accelerating agent, sulfide, fluoride etc. can be used.
It, can be suitably using chloride, sulfide, itrated compound, 2,2- bipyridyls, the 2- sulfydryls of lead as aforementioned stable agent Benzothiazole, nicotine etc..
By above-mentioned electroless plating facture be laminated in above-mentioned wet type Polyester non-woven fabrics base material it is surface, be preferably The metals such as copper have superior adaptation and electric conductivity, in terms of the cost needed for above-mentioned processing is reduced, preferably in 1g/m2 ~20g/m2Scope, more preferably in 3g/m2~10g/m2Scope, further preferably in 5g/m2~8g/m2Scope.
Conductive substrate used in the present invention, as described above, it is preferred to using to wet type Polyester nonwoven fabric base Material further carries out base material obtained from electroless plating or electrolytic coating processing after carrying out electroless metal deposition processing, Coating can be stably formed within a short period of time especially with base material obtained from being handled through electrolytic coating, it is thus possible to be dropped Low production cost can simultaneously realize high intensity, so more preferably.
As the electrolytic coating liquid that can be used in the processing of above-mentioned electrolytic coating, can use for example including pyrophosphoric acid Copper, copper cyanide bath, copper sulphate bath etc. copper plating bath, including watt bath, chlorination bath, sulfamic acid bathe etc. nickel-plating liquid, including Sa Jin Te bathes (Japanese：Mono- ジ エ Application ト of サ are bathed) etc. chromium plating liquid or plating liquid containing gold, silver, tin, zinc etc..
As above-mentioned conductive substrate, using its outermost layer for the coating containing nickel base material then excellent storage stability, The excellent and excellent electric conductivity in terms of the adaptation of wet type Polyester non-woven fabrics base material and coating, so it is preferred that.
Above-mentioned outermost layer preferably comprises 1g/m2~10g/m2Nickel, further preferably 2g/m2~8g/m2, contain 2.5g/m2 ~6g/m2It is then further preferred in terms of above-mentioned excellent storage stability, adaptation, electric conductivity is taken into account.
As the preferred embodiment of above-mentioned conductive substrate, can enumerate for example real successively to wet type Polyester non-woven fabrics base material It is conductive substrate obtained from applying electroless plating Copper treatment and electrolytic ni plating processing, real successively to wet type Polyester non-woven fabrics base material Apply electroless plating Copper treatment, electrolytic copper plating processing and conductive substrate obtained from electrolytic ni plating processing.
Next, the conductive adhesive oxidant layer of the electroconductive adhesive sheet to forming the present invention illustrates.
Above-mentioned conductive adhesive oxidant layer is containing compared with the matter of above-mentioned conductive adhesive oxidant layer generally 3 mass %~50 Measure the adhesive phase of the electroconductive particle of %.Electroconductive adhesive sheet with the conductive adhesive oxidant layer is with excellent conduction Property.
As above-mentioned conductive adhesive oxidant layer, it is preferable to use containing compared with above-mentioned conductive adhesive oxidant layer generally 5 matter Measure the adhesive phase of the electroconductive particle of the mass % of %~50, more preferably using containing 10 mass %~50 mass % electric conductivity The adhesive phase of particle, using containing 15 mass %~45 mass % electroconductive particle adhesive phase can then show it is more excellent Different electric conductivity, the horizontal flexibility and re-workability that differential portion etc. possessed by adherend can be followed, so it is excellent Choosing.
As above-mentioned conductive adhesive oxidant layer, it is preferable to use the adhesive phases of 3 μm~25 μ m thicks, more preferably use 5 μm The adhesive phase of~20 μ m thicks can then be obtained using the adhesive phase of 7 μm~18 μ m thicks and take into account superior bonding Property and slimming electroconductive adhesive sheet.
It, can be by using the adhesive containing electroconductive particle and adhesive ingredients as above-mentioned conductive adhesive oxidant layer Composition is formed.
As the electroconductive particle contained by above-mentioned conductive adhesive oxidant layer, the gold such as gold, silver, copper, nickel, aluminium can be used Belong to electroconductive resins particle, above-mentioned resin, solid glass pearl, the surfaces of Hollow Glass Sphere such as particle, carbon, graphite by coating metal Particle formed etc..Wherein, as above-mentioned electroconductive particle, using nickel particles, copper particle, silver particles then with superior Electric conductivity and adhesive strength and make electroconductive adhesive sheet productivity further improve aspect be preferred.
In addition, as above-mentioned electroconductive particle, can enumerate for example by the particle surface that carbonyl process manufactures with multiple The nickel particles of the surface needle-like shape of needle-like shape carry out smoothing techniques to the surface acicular particles and spherical particle are made Particle, copper particle, the silver particles manufactured by super-pressure rotary spray method (super-pressure cycle water ア ト マ イ ズ methods).
As above-mentioned electroconductive particle, it is preferable to use spherical or surface needle-like shape particles.As above-mentioned electric conductivity grain Son, it is further excellent more preferably using the particle with 1~1.5 aspect ratio it is preferable to use the particle with 1~2 aspect ratio Choosing uses the particle with 1~1.2 aspect ratio.Above-mentioned aspect ratio can be led by using scanning electron microscope to above-mentioned It is observed to measure in the surface of conductive particles.
As above-mentioned electroconductive particle, using with 2g/cm3~7g/cm3Tap density particle then formed it is conductive Property adhesive phase when be difficult to happen sedimentation, aggegation, so it is preferred that, more preferably using have 3g/cm3~6g/cm3Tap density Particle, further preferably using have 4g/cm3~5g/cm3Tap density particle.
As above-mentioned electroconductive particle, it is preferable to use its grain size d50 be 3 μm~20 μm and its grain size d85 is 6 μm~40 μm Particle.
The above-mentioned grain size d50 of above-mentioned electroconductive particle is more preferably 4 μm~15 μm, further preferably 5 μm~12 μm, special It You Xuanwei not be 6 μm~10 μm.
In addition, the above-mentioned grain size d85 of above-mentioned electroconductive particle is more preferably 8 μm~30 μm, further preferably 9 μm~25 μm, particularly preferably 10 μm~20 μm.Wherein, when electroconductive particle of more than two kinds is applied in combination, it is preferable to use the mixed of them Close particles of the average grain diameter d50 and d85 in above range of object.
Wherein, above-mentioned grain size d50 represents 50% aggregate-value (median particle diameter) in size distribution, and above-mentioned grain size d85 is represented 85% aggregate-value.Specifically, above-mentioned grain size is the value by laser desorption-scattering method.Refer to Shimano Inc It is the value that measurement device measures to make made laser diffraction formula particle size distribution device SALD-3000.
As above-mentioned electroconductive particle, the thickness that above-mentioned grain size d50 is above-mentioned conductive adhesive oxidant layer is preferably selected 50%~150% particle, more preferably selects the particle for 60%~120%, further preferably selects as 70%~100% Particle.
In addition, as above-mentioned electroconductive particle, the thickness that above-mentioned grain size d85 is above-mentioned conductive adhesive oxidant layer is more preferably selected 80%~200% particle of degree, more preferably selects the particle for 100%~150%, further preferably select as 110%~ 140% particle.
By using the electroconductive particle of above-mentioned grain size d50 and d85, electric conductivity and adhesive strength are more excellent, and can make The production efficiency of electroconductive adhesive sheet further improves.
Above-mentioned electroconductive particle preferably compared with contained by above-mentioned conductive adhesive oxidant layer adhesive ingredients (solid-state into Point) 100 mass parts is use in the range of the mass parts of 5 mass parts~100, the model more preferably in the mass parts of 10 mass parts~100 Interior use is enclosed, it is more excellent using then electric conductivity and adhesive strength in the range of the mass parts of 20 mass parts~80 and conduction can be made Property bonding sheet production efficiency further improve, thus particularly preferably.Specifically, above-mentioned electroconductive particle preferably compared with 100 mass parts of acrylic acid series polymeric compounds (solid state component) contained by above-mentioned conductive adhesive oxidant layer are the mass parts of 5 mass parts~100 In the range of use, more preferably used in the range of the mass parts of 10 mass parts~100, in the model of the mass parts of 20 mass parts~80 It encloses interior more excellent using then electric conductivity and adhesive strength and can further improve the production efficiency of electroconductive adhesive sheet, thus Particularly preferably.
As the method for mixing above-mentioned electroconductive particle and above-mentioned adhesive ingredients, can enumerate electric conductivity object for example The method of the mixing such as adhesive ingredients and above-mentioned additive such as matter, acrylic acid series polymeric compounds as adhesive ingredients.It is above-mentioned The adhesive ingredients such as acrylic acid series polymeric compounds and solvent and additive as needed can be pre-mixed.Above-mentioned mixing can make With dispersing mixers such as dissolvers, butterfly mixer, BDM double-screw mixers, epicyclic mixers.Wherein, it is preferable to use can Application can inhibit the dissolvers of the moderate shearing force of the rising of viscosity, butterfly mixer during above-mentioned mixing.
In addition, as the adhesive ingredients for forming above-mentioned conductive adhesive oxidant layer, can be bonded using such as acrylic acid series Agent composition, silicon-type adhesive composition, elastomeric adhesive composition etc..Wherein, as above-mentioned adhesive ingredients, Realize electroconductive adhesive sheet production cost reduction and cementability further improve aspect, it is preferable to use acrylic adhesives Composition.
As aforesaid propylene acid system adhesive composition, such as composition containing acrylic acid series polymeric compounds can be used.
As aforesaid propylene acid based polymer, can use make polymer obtained from polymerizing monomer components.
As above-mentioned monomer component, (methyl) propylene for example containing the alkyl with carbon number 1~14 can be used The monomer component of acid esters.
As (methyl) acrylate of the above-mentioned alkyl with carbon number 1~14, such as can be used alone or group It closes using (methyl) methyl acrylate of more than two kinds, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) third The different monooctyl ester of olefin(e) acid, the different nonyl ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) 2-EHA etc..
Wherein, (methyl) acrylate as the above-mentioned alkyl with carbon number 1~14, it is preferable to use former with carbon (methyl) acrylate of the alkyl of subnumber 4~12 more preferably uses the (first of the straight or branched alkyl of carbon number 4~9 Base) acrylate, further preferably 2 kinds of n-butyl acrylate, 2-EHA exclusive use or combination are used.
(methyl) acrylate of the above-mentioned alkyl with carbon number 1~14 is preferably compared with above-mentioned monomer component Total amount more preferably makes to be used in the range of the mass % of 80 mass %~98.5 in the range of the mass % of 90 mass %~98.5 With.
In addition, when manufacturing the acrylic acid series polymeric compounds used in the present invention, polar vinyl monomer can be used as upper State monomer component.As above-mentioned polar vinyl monomer, can use the one kind or two or more vinyl monomer with hydroxyl, Vinyl monomer with carboxyl, vinyl monomer with amide groups etc..
As the vinyl monomer with carboxyl, acrylic acid, methacrylic acid, itaconic acid, maleic acid, (first can be used Base) acrylic acid dimer, crotonic acid, ethylene-oxide-modified succinic acid acrylate etc., wherein, it is preferable to use acrylic acid or methyl Acrylic acid, more preferably using acrylic acid.
It is 1 mass % preferably in the total amount compared with above-mentioned monomer component as the above-mentioned vinyl monomer with carboxyl It is used in the range of~10 mass %, more preferably the mass % of 1.5 mass %~6, is the mass % of 2 mass %~4 then to forming The initial bond strenght of the metal covering of adherend is excellent, and even if hot and humid inferior conductive adhesive adhesive tape is stored in When, the excellent adhesive strength to adherend can be also shown, thus further preferably.In addition, there is carboxyl as above-mentioned Vinyl monomer and preferred acrylic acid in the total amount compared with above-mentioned monomer component is the scope of the mass % of 1 mass %~6 It is interior to use the superior wetability and adhesive strength that then take into account to adherend, so it is preferred that.
As the above-mentioned vinyl monomer with hydroxyl, such as (methyl) acrylic acid 2- hydroxy methacrylates, (first can be used Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, the own ester of (methyl) acrylic acid 6- hydroxyls etc. have hydroxyl (methyl) acrylate.
As the above-mentioned vinyl monomer with amide groups, such as n-vinyl pyrrolidone, N- vinyl can be used Caprolactam, acryloyl morpholine, acrylamide, N,N-DMAA etc..
As other vinyl monomers, can use for example vinyl acetate, ethylene-oxide-modified succinic acid acrylate, 2- acrylamide-2-methyl propane sulfonics etc. contain sulfonic monomer, (methyl) acrylic acid 2- methoxy acrylates, (methyl) propylene The end alkoxy groups such as sour 2- phenoxy ethyls are modified (methyl) acrylate etc..
Above-mentioned polar vinyl monomer is the mass % of 0.2 mass %~15 preferably in the total amount compared with above-mentioned monomer component In the range of use, more preferably used in the range of the mass % of 0.4 mass %~10, in the model of the mass % of 0.5 mass %~6 Interior use is enclosed then easily to adjust adhesive strength to appropriate scope, thus further preferably.
Aforesaid propylene acid based polymer can be by using solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization Method well known to method etc. makes above-mentioned polymerizing monomer components and manufactures, wherein, from the reduction and production efficiency for realizing production cost In terms of raising, it is preferred to use solution polymerization process.
As the acrylic acid series polymeric compounds obtained by the above method, it is preferable to use divide equally again with 300,000~1,500,000 The polymer of son amount, more preferably using the polymer with 500,000~1,200,000 weight average molecular weight.
In terms of cohesive force is further improved, realize the superior effect of cementability, preferably above-mentioned conductive adhesive oxidant layer Form three-dimensional crosslinking structure.
On above-mentioned crosslinked degree, as its index, can use as the good molten of aforesaid propylene acid based polymer The gel fraction represented by insoluble component after when dipping 24 is small in the toluene of agent identifies.As above-mentioned conductive adhesive Layer is the adhesive phase of the mass % of 25 mass %~65 it is preferable to use its gel fraction, more preferably using for 35 mass %~60 The adhesive phase of quality %, using the adhesive phase for the mass % of 40 mass %~55 can then make shear direction cohesive force and Spalling resistance is more preferable, thus further preferably.
Wherein, above-mentioned gel fraction can be calculated by following formula.
Gel fraction (quality %)=(the adhesive phase quality after being impregnated in toluene)/it is (viscous before being impregnated in toluene Mixture layer quality) } × 100
Adhesive phase quality=(quality of electroconductive adhesive sheet)-(quality of base material)-(quality of electroconductive particle)
When forming the conductive adhesive oxidant layer with above-mentioned cross-linked structure, as adhesive, it is preferable to use for example containing upper State acrylic acid series polymeric compounds etc. and the simultaneously adhesive containing crosslinking agent.
As above-mentioned crosslinking agent, such as isocyanates system crosslinking agent, epoxy crosslinking agent, chelate system can be used to be crosslinked Agent, aziridine system crosslinking agent etc..On the species of above-mentioned crosslinking agent, it is preferable to use had corresponding to aforesaid propylene acid based polymer The crosslinking agent of some functional groups.For example, when using the polymer with carboxyl as aforesaid propylene acid based polymer, isocyanide is used Acid esters system crosslinking agent is suitable.
Above-mentioned crosslinking agent preferably selects the amount of the above-mentioned gel fraction of above-mentioned conductive adhesive oxidant layer within the above range.
So that for the purpose of its bonding force further improves, above-mentioned conductive adhesive oxidant layer can contain tackifying resin.
As above-mentioned tackifying resin, such as rosin series resin, terpene system resin, aliphatic (C5 systems), aromatic series can be used Petropols such as (C9 systems), phenylethylene resin series phenolic aldehyde system resin, diformazan benzene series resin, metha crylic resin etc..Wherein, As above-mentioned tackifying resin, it is preferable to use rosin series resins, more preferably use newtrex system resin.Compared with 100 mass parts (methyl) acrylic acid series polymeric compounds, the usage amount of above-mentioned tackifying resin is preferably in the scope of the mass parts of 10 mass parts~50.
Above-mentioned conductive adhesive oxidant layer can contain various additives as needed.
As above-mentioned additive, such as plasticizer, softening agent, metal deactivator, antioxidant, pigment, dye can be used Material etc..
As the adhesive that can be used in the formation of above-mentioned conductive adhesive oxidant layer, can use containing specified amount The adhesive of above-mentioned conductive material and above-mentioned adhesive ingredients.
In addition, as above-mentioned conductive adhesive oxidant layer, the adhesive phase containing three azole compounds can be used.
As above-mentioned triazole compounds, such as benzotriazole, tolyl-triazole and its sylvite, 3- (N- bigcatkin willows can be used Acyl group) amino -1,2,4-triazoles, 2- (2 '-hydroxyl, 5 aminomethyl phenyl) benzotriazole etc., it can inhibit excellent using benzotriazole It is bonded the reduction of retentivity and the reduction of adhesive strength that while being positioned under hot and humid environment can occur, thus particularly preferably.
Compared with 100 mass parts of acrylic adhesive composition (solid state component), above-mentioned three azole compounds preferably exist It uses in the range of the mass parts of 0.05 mass parts~3.0, is more preferably used in the range of the mass parts of 0.1 mass parts~1.5, Using the reduction that can inhibit excellent bonding retentivity and high temperature height is positioned in the range of the mass parts of 0.3 mass parts~1.0 The reduction for the adhesive strength that can occur when under wet environment, thus further preferably.
The adhesive obtained by the above method can be exclusively used in the formation of conductive adhesive oxidant layer.Above-mentioned adhesive is consolidated State ingredient is preferably in the scope of the mass % of 10 mass %~70, the scope more preferably in the mass % of 30 mass %~55, further It is preferred that in the scope of the mass % of 43 mass %~50.
The electroconductive adhesive sheet of the present invention can for example be manufactured through following processes：It will be above-mentioned using roll coater, die coating machine etc. Adhesive is coated on the surface of stripping film, and the coating layer is made to be dried in the environment of 50 DEG C~120 DEG C or so and removes solvent, So as to form the process of conductive adhesive layer；Next conductive adhesive layer is laminated in the two sides of above-mentioned conductive substrate, root According to needing to carry out the processes such as heat lamination；Next as needed with 15 DEG C~50 DEG C or so of temperature maintenance 48 it is small when~it is 168 small When or so process.
Above-mentioned heat lamination preferably in 40 DEG C~120 DEG C progress, more preferably in 50 DEG C~100 DEG C progress, further preferably exists 60 DEG C~90 DEG C progress.
In addition, the electroconductive adhesive sheet as the present invention, can be that film is laminated with before it is adhered to adherend Bonding sheet.
As above-mentioned stripping film, the paper such as brown paper, cellophane paper, good quality paper can be used；Polyethylene, polypropylene The resin films such as (OPP, CPP), polyethylene terephthalate；By above-mentioned paper and resin film lamination form laminated paper, with There is the one or both sides of paper obtained from soil, polyvinyl alcohol etc. implement above-mentioned paper filling processing (mesh stops め processing) Paper etc. obtained from the lift-off processings such as machine silicon system resin.
The example preferably comprised of the electroconductive adhesive sheet of the present invention is shown in Fig. 1 and Fig. 2.Fig. 1 is in conductive substrate 1 The upper single side bonding sheet for being stacked conductive adhesive layer 2 and forming.In addition, Fig. 2 is the two sides laminated conductive in conductive substrate 1 The double-sided adhesive sheet that adhesive phase 2 forms.It is preferable to use be equipped with stripping film on the surface of adhesive phase 2 during these are formed Composition.
The flexibility of the electroconductive adhesive sheet of the present invention is excellent, have to the good cementability of adherend, electric conductivity with And re-workability, therefore use, prevent the ground connection of electrostatic from fixing with being as electromagnetic wave shielding used in electrical, electronic equipment etc. Useful.It enables in particular to be appropriately used for being pasted onto mancarried electronic aid there are convex-concave portion, being difficult to paste electroconductive adhesive sheet Wait the purposes used on the build-in components of miniature electrics terminal.
Embodiment
It is concretely demonstrated below based on embodiment.
Production Example 1 [conductive substrate (A)]
By wet type polyester non-woven fabric " type A " (weight per unit area 10g/m of three wooden Tokushu Paper MFG. Co., Ltd.2, it is thick Spend 15 μm, the diameter 5 μm (average diameters) of polyester fiber) room temperature in the aqueous solution containing 10g/l stannic chlorides, 20ml/l hydrochloric acid Dipping about 5 minutes, is then washed.
Next, room temperature soaks in the aqueous solution containing 1g/l palladium bichlorides and 20ml/l hydrochloric acid by the above-mentioned material through washing Stain about 10 minutes, is then washed.
Next, by the above-mentioned material through washing containing 10g/l copper sulphate, 7ml/l formaldehyde, 8g/l sodium hydroxides, 30g/l tetrasodium ethylenediamine tetraacetates (EDTA-4Na) and 0.25ml/l stabilizers, adjust into 40 DEG C of electroless plating covering liquid Dipping 20 minutes, is followed by washed, so as to obtain the wet type polyester non-woven fabric through electroless plating.
Next, by the above-mentioned wet type polyester non-woven fabric through electroless plating in electrolytic copper plating liquor (pharmacy work in open country difficult to understand Industry Co. Ltd. system, Toppuruchina (ト Star プ Le チ Na) SF) in dipping, carry out electrolytic copper plating processing so that above-mentioned electrolysis The plating amount for the copper that copper plating bath is brought is 6g/m2, so as to obtain the wet type polyester non-woven fabric handled through electrolytic copper plating.
Next, the above-mentioned wet type polyester non-woven fabric handled through electrolytic copper plating is being contained into 240g/l nickel sulfates, 45g/l chlorine Change and impregnated in the electrolytic ni plating liquid of nickel, 30g/l boric acid, 2g/l saccharin and 0.2g/l1,4- butynediols, carried out at electrolytic ni plating It manages so that the plating amount for the nickel that above-mentioned electrolytic ni plating liquid band is come is 4g/m2, wash and dry, so as to make conductive substrate (A).
Production Example 2 [conductive substrate (B)]
Use wet type polyester non-woven fabric " Silky Fine WS7A-05-6 " (unit area weight of Asahi Kasei Corporation Measure 6g/m2, 18 μm of thickness, the diameter 4.5 μm (average diameters) of polyester fiber) replace the wet of three wooden Tokushu Paper MFG. Co., Ltd. Formula polyester non-woven fabric " type A ", in addition, by with 1 same method of Production Example, make conductive substrate (B).
Production Example 3 [conductive substrate (C)]
Use wet type polyester non-woven fabric " Silky Fine WS7A-04 " (weight per unit area of Asahi Kasei Corporation 4g/m2, 16 μm of thickness, the diameter 4.5 μm (average diameters) of polyester fiber) replace the wet type of three wooden Tokushu Paper MFG. Co., Ltd. Polyester non-woven fabric " type A ", in addition, by with 1 same method of Production Example, make conductive substrate (C).
Production Example 4 [conductive substrate (D)]
Use this System of Nippon Paper papylia Co., Ltd. (パ ピ リ ア Co., Ltd.) system wet type non-woven polyester Cloth " 5.5g/m2" (weight per unit area 5.5g/m2, 14 μm of thickness, the diameter 4.5 μm (average diameters) of polyester fiber) replace three The wet type polyester non-woven fabric " type A " of wooden Tokushu Paper MFG. Co., Ltd., in addition, by with 1 same method of Production Example, Make conductive substrate (D).
Production Example 5 [conductive substrate (E)]
By wet type polyester non-woven fabric " type A " (weight per unit area of three wooden Tokushu Paper MFG. Co., Ltd. under room temperature 10g/m2, 15 μm of thickness, the diameter 5 μm (average diameters) of polyester fiber) in the water containing 10g/l stannic chlorides and 20ml/l hydrochloric acid It impregnates about 5 minutes, after washing, is impregnated in the aqueous solution containing 1g/l palladium bichlorides and 20ml/l hydrochloric acid about 10 minutes in solution, Washing.
Next, by the above-mentioned material through washing containing 10g/l copper sulphate, 7ml/l formaldehyde, 8g/l sodium hydroxides, 30g/l tetrasodium ethylenediamine tetraacetates (EDTA-4Na) and stabilizer (0.25ml/l), adjust to 40 DEG C of electroless plating covering liquid Middle dipping 60 minutes, the plating amount of the copper brought using above-mentioned electroless plating covering liquid is 6g/m2Mode carry out at electroless plating After reason, wash and dry, so as to make conductive substrate (E).
Production Example 6 [conductive substrate (F)]
By wet type polyester non-woven fabric " type A " (weight per unit area of three wooden Tokushu Paper MFG. Co., Ltd. under room temperature 10g/m2, 15 μm of thickness, the diameter 5 μm (average diameters) of polyester fiber) in the water containing 10g/l stannic chlorides and 20ml/l hydrochloric acid It impregnates about 5 minutes, after washing, is impregnated in the aqueous solution containing 1g/l palladium bichlorides and 20ml/l hydrochloric acid about 10 minutes in solution, Washing.
Next, the above-mentioned material through washing is being contained into 20g/l nickel sulfates, 30g/l sodium citrates, 15g/l hypophosphorous acid Sodium and 30g/l ammonium chlorides, adjusted with ammonium hydroxide and impregnated 60 minutes into 40 DEG C of pH9.5 of electroless plating covering liquid, with above-mentioned nothing The plating amount for the nickel that electrolytic coating liquid band is come is 6g/m2Mode carry out electroless plating after, wash it is simultaneously dry, so as to make Make conductive substrate (F).
Production Example 7 [conductive substrate (G)]
By wet type polyester non-woven fabric " type A " (weight per unit area of three wooden Tokushu Paper MFG. Co., Ltd. under room temperature 10g/m2, 15 μm of thickness, the diameter 5 μm (average diameters) of polyester fiber) in the water containing 10g/l stannic chlorides and 20ml/l hydrochloric acid It impregnates about 5 minutes, after washing, is impregnated in the aqueous solution containing 1g/l palladium bichlorides and 20ml/l hydrochloric acid about 10 minutes in solution, Washing.
Next, by the above-mentioned material through washing containing 10g/l copper sulphate, 7ml/l formaldehyde, 8g/l sodium hydroxides, 30g/l tetrasodium ethylenediamine tetraacetates (EDTA-4Na) and stabilizer (0.25ml/l), adjust to 40 DEG C of electroless plating copper liquid Middle dipping 60 minutes, the plating amount of the copper brought using above-mentioned electroless plating copper liquid is 6g/m2Mode carry out at electroless copper facing It after reason, is washed, so as to obtain the wet type polyester non-woven fabric through electroless plating Copper treatment.
Next, the above-mentioned wet type polyester non-woven fabric through electroless plating Copper treatment is being contained into 20g/l nickel sulfates, 30g/l Sodium citrate, 15g/l sodium hypophosphites and 30g/l ammonium chlorides, adjusted into 40 DEG C of pH9.5 of electroless nickel plating solution with ammonium hydroxide Dipping 30 minutes, the plating amount of the nickel brought using above-mentioned electroless nickel plating solution is 4g/m2Mode carry out electroless nickel plating processing After washed, so as to make conductive substrate (G).
Production Example 8 [conductive substrate (H)]
By wet type polyester non-woven fabric " type A " (weight per unit area 10g/m of three wooden Tokushu Paper MFG. Co., Ltd.2, it is thick Spend 15 μm, the diameter 5 μm (average diameters) of polyester fiber) room temperature in the aqueous solution containing 10g/l stannic chlorides, 20ml/l hydrochloric acid Dipping about 5 minutes, is then washed.
Next, room temperature soaks in the aqueous solution containing 1g/l palladium bichlorides and 20ml/l hydrochloric acid by the above-mentioned material through washing Stain about 10 minutes, is then washed.
Next, by the above-mentioned material through washing containing 10g/l copper sulphate, 7ml/l formaldehyde, 8g/l sodium hydroxides, 30g/l tetrasodium ethylenediamine tetraacetates (EDTA-4Na) and 0.25ml/l stabilizers, adjust into 40 DEG C of electroless plating covering liquid Dipping 20 minutes, is followed by washed, so as to obtain the wet type polyester non-woven fabric through electroless plating.
Next, the above-mentioned wet type polyester non-woven fabric through electroless plating is being contained into 240g/l nickel sulfates, 45g/l Nickel chloride, 30g/l boric acid, 2g/l saccharin and 0.2g/l1,4- butynediols electrolytic ni plating liquid in impregnate, plated with above-mentioned electrolysis The plating amount for the nickel that nickel liquid band is come is 4g/m2Mode carry out electrolytic ni plating processing, wash it is simultaneously dry, so as to make electric conductivity base Material (H).
Production Example 9 [conductive substrate (I)]
With Asahi Chemical Ind Precis é (carrying out copper and mickel plating to dry type polyester non-woven fabric to form) As conductive substrate (I).
Production Example 10 [conductive substrate (J)]
Use the dry type polyester non-woven fabric " MILIFE of JX Nippon Oil＆Energy Corporation TY0503FE " (weight per unit area 8g/m2, 28 μm of thickness, the diameter 12 μm (average diameters) of polyester fiber) replace three wood special The wet type polyester non-woven fabric " type A " of paper Co. Ltd. system kind processed, in addition, by with 1 same method of Production Example, make Conductive substrate (J).
Production Example 11 [conductive substrate (K)]
[plating non-woven fabrics K]
It is (single using the dry type polyester non-woven fabric " MILIFE T10 " of JX Nippon Oil＆Energy Corporation Position area weight 10g/m2, 28 μm of thickness, the diameter 10 μm (average diameters) of polyester fiber) replace three wooden special type paper strain formula meetings The wet type polyester non-woven fabric " type A " of society, in addition, by with 1 same method of Production Example, make conductive substrate (K)。
Production Example 12 [conductive substrate (L)]
Use wet type fiber crops non-woven fabrics " D54E " (weight per unit area 16g/m of Nippon Paper papylia Co. Ltd. systems2、 43 μm of thickness) replace the wet type polyester non-woven fabric " type A " of three wooden Tokushu Paper MFG. Co., Ltd., in addition, by with system 1 same method of example is made, makes conductive substrate (L).
Preparation example 1 [preparation of acrylic adhesive composition (1)]
In the reaction vessel for possessing condenser pipe, mixer, thermometer, dropping funel, by 96.4 mass parts acrylic acid just Butyl ester, 0.1 mass parts acrylic acid 2- hydroxyl ethyl esters, 3.5 mass parts acrylic acid and 0.1 mass parts as polymerization initiator 2, 2 '-azodiisobutyronitrile is dissolved in 100 mass parts ethyl acetate, after carrying out nitrogen displacement in reaction vessel, in 80 DEG C of polymerizations 12 it is small when, so as to obtain the acrylic acid series copolymer solution of weight average molecular weight 600,000.
Compared with 100 mass parts of solid state component of aforesaid propylene acid based copolymer solution, coordinate 10 mass parts newtrexes Pentaerythritol ester (Arakawa Chemical Industries (strain) system, Pensel D-135,135 DEG C of softening point), 10 mass parts disproportionated rosin glycerine Ester (Arakawa Chemical Industries (strain) system, Super Ester A-100,100 DEG C of softening point) is sour by aforesaid propylene using ethyl acetate The solid component concentration of based copolymer is adjusted to 45 mass %, so as to obtain acrylic adhesive composition (1).
Preparation example 2 [preparation of acrylic adhesive composition (2)]
In the reaction vessel for possessing condenser pipe, mixer, thermometer, dropping funel, by 99.9 mass parts acrylic acid just Butyl ester, 0.1 mass parts acrylic acid 2- hydroxyl ethyl esters, 0.1 mass parts as polymerization initiator 2,2 '-azodiisobutyronitrile is dissolved in 100 mass parts ethyl acetate, after carrying out nitrogen displacement in reaction vessel, when 80 DEG C of polymerizations 12 are small, so as to be divided equally again The acrylic acid series copolymer solution of son amount 600,000.
Compared with 100 mass parts of solid state component of aforesaid propylene acid based copolymer solution, coordinate 10 mass parts newtrexes Pentaerythritol ester (Arakawa Chemical Industries (strain) system, Pensel D-135,135 DEG C of softening point), 10 mass parts disproportionated rosin glycerine Ester (Arakawa Chemical Industries (strain) system, Super Ester A-100,100 DEG C of softening point) is sour by aforesaid propylene using ethyl acetate The solid component concentration of based copolymer is adjusted to 45 mass %, so as to obtain acrylic adhesive composition (2).
Preparation example 3 [preparation of acrylic adhesive composition (3)]
In the reaction vessel for possessing condenser pipe, mixer, thermometer, dropping funel, by 92.9 mass parts acrylic acid just Butyl ester, 0.1 mass parts acrylic acid 2- hydroxyl ethyl esters, 7 mass parts acrylic acid, 0.1 mass parts as polymerization initiator 2,2 '-azo Bis-isobutyronitrile is dissolved in 100 mass parts ethyl acetate, after carrying out nitrogen displacement in reaction vessel, when 80 DEG C of polymerizations 12 are small, So as to obtain the acrylic acid series copolymer solution of weight average molecular weight 600,000.
Compared with 100 mass parts of solid state component of aforesaid propylene acid based copolymer solution, coordinate 10 mass parts newtrexes Pentaerythritol ester (Arakawa Chemical Industries (strain) system, Pensel D-135,135 DEG C of softening point), 10 mass parts disproportionated rosin glycerine Ester (Arakawa Chemical Industries (strain) system, Super Ester A-100,100 DEG C of softening point) is sour by aforesaid propylene using ethyl acetate The solid component concentration of based copolymer is adjusted to 45 mass %, so as to obtain acrylic adhesive composition (3).
Preparation example 4 [preparation of acrylic adhesive composition (4)]
In the reaction vessel for possessing condenser pipe, mixer, thermometer, dropping funel, by 97.4 mass parts acrylic acid just 2, the 2 '-idol of butyl ester, 0.1 mass parts acrylic acid 2- hydroxyl ethyl esters, 2.5 mass parts acrylic acid, 0.1 mass parts as polymerization initiator Nitrogen bis-isobutyronitrile is dissolved in 100 mass parts ethyl acetate, small in 80 DEG C of polymerizations 12 after carrying out nitrogen displacement in reaction vessel When, so as to obtain the acrylic acid series copolymer solution of weight average molecular weight 600,000.
Compared with 100 mass parts of solid state component of aforesaid propylene acid based copolymer solution, coordinate 10 mass parts newtrexes Pentaerythritol ester (Arakawa Chemical Industries (strain) system, Pensel D-135,135 DEG C of softening point), 10 mass parts disproportionated rosin glycerine Ester (Arakawa Chemical Industries (strain) system, Super Ester A-100,100 DEG C of softening point) is sour by aforesaid propylene using ethyl acetate The solid component concentration of based copolymer is adjusted to 45 mass %, so as to obtain acrylic adhesive composition (4).
Preparation example 5 [preparations of conductive adhesive compositions (1A-1)]
By 100 mass parts aforesaid propylene acid system's adhesive compositions (1) (45 mass % of solid state component), 22.5 mass parts good fortune Nickel powder " NI123J " (grain size d50 of field metal foil powder Industrial Co., Ltd：6.3 μm, grain size d85：10.0 μm, tap density： 4.3g/cm3, smoothing techniques are carried out to Inco Limited " NI123 " and are obtained), 2.5 mass parts are as crosslinking agent BURNOCK NC40 (the isocyanates system crosslinking agent, 40 mass % of solid state component of Dainippon Ink Chemicals) and 0.23 mass parts Benzotriazole mixes, and is adjusted solid component concentration to 47 mass % with ethyl acetate, 10 are stirred to it using dispersator Minute, so as to obtain conductive adhesive (1A-1).
Preparation example 6 [preparations of conductive adhesive compositions (1A-2)]
The usage amount of the nickel powder " NI123J " of Fukuda Metal Foil ＆ POwder Co., Ltd. is changed to 9 by 22.5 mass parts Mass parts, in addition, by with 5 same method of preparation example, obtain conductive adhesive (1A-2).
Preparation example 7 [preparations of conductive adhesive compositions (1A-3)]
The usage amount of the nickel powder " NI123J " of Fukuda Metal Foil ＆ POwder Co., Ltd. is changed to by 22.5 mass parts 36 mass parts, in addition, by with 5 same method of preparation example, obtain conductive adhesive (1A-3).
Preparation example 8 [preparations of conductive adhesive compositions (1A-4)]
The usage amount of the nickel powder " NI123J " of Fukuda Metal Foil ＆ POwder Co., Ltd. is changed to 0 by 22.5 mass parts Mass parts, in addition, by with 5 same method of preparation example, obtain conductive adhesive (1A-4).
Preparation example 9 [preparations of conductive adhesive compositions (1A-5)]
The usage amount of the nickel powder " NI123J " of Fukuda Metal Foil ＆ POwder Co., Ltd. is changed to by 22.5 mass parts 67.5 mass parts, in addition, by with 5 same method of preparation example, obtain conductive adhesive (1A-5).
Preparation example 10 [preparations of conductive adhesive compositions (2A)]
Using aforesaid propylene acid system adhesive composition (2) replace aforesaid propylene acid system adhesive composition (1), except this with Outside, by with 5 same method of preparation example, obtain conductive adhesive (2A).
Preparation example 11 [preparations of conductive adhesive compositions (3A)]
Using aforesaid propylene acid system adhesive composition (3) replace aforesaid propylene acid system adhesive composition (1), except this with Outside, by with 5 same method of preparation example, obtain conductive adhesive (3A).
Preparation example 12 [preparations of conductive adhesive compositions (4A)]
Using aforesaid propylene acid system adhesive composition (4) replace aforesaid propylene acid system adhesive composition (1), except this with Outside, by with 5 same method of preparation example, obtain conductive adhesive (4A).
Preparation example 13 [preparations of conductive adhesive compositions (1B)]
Use nickel powder " NI123 " (grain size d50 of 22.5 mass parts Inco Limited：10.7th, grain size d85： 25.0 μm) instead of the nickel powder " NI123J " of Fukuda Metal Foil ＆ POwder Co., Ltd., in addition, by same with preparation example 5 The method of sample obtains conductive adhesive (1B).
(embodiment 1)
Using comma coater by above-mentioned conductive adhesive compositions (1A-1) with dried conductive adhesive oxidant layer Thickness be coated on NIPPA CO. as 9 μm of mode, on the stripping film " PET38 × 1A3 " of LTD., using being set in 80 DEG C drier dry 2 minutes, so as to make conductive adhesive oxidant layer.
Next, above-mentioned conductive adhesive oxidant layer is pasted on to the two sides of above-mentioned conductive substrate (A), with 80 DEG C to them Heat lamination is carried out, next, when 40 DEG C of maintenances 48 are small, so as to make electroconductive adhesive sheet.
(embodiment 2)
Conductive substrate (A) is replaced using conductive substrate (B), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(embodiment 3)
Conductive substrate (A) is replaced using conductive substrate (C), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(embodiment 4)
Conductive substrate (A) is replaced using conductive substrate (D), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(embodiment 5)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (1A-2), in addition, are led to It crosses and applies 1 same method of example, make electroconductive adhesive sheet.
(embodiment 6)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (1A-3), in addition, are led to It crosses and applies 1 same method of example, make electroconductive adhesive sheet.
(embodiment 7)
Using conductive adhesive compositions (2A) replace conductive adhesive compositions (1A-1), and by curing time by 48 be changed to when small 120 it is small when, in addition, by with applying 1 same method of example, making electroconductive adhesive sheet.
(embodiment 8)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (3A), in addition, are passed through With applying 1 same method of example, electroconductive adhesive sheet is made.
(embodiment 9)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (4A), in addition, are passed through With applying 1 same method of example, electroconductive adhesive sheet is made.
(embodiment 10)
The thickness of conductive adhesive oxidant layer is changed to 7 μm by 9 μm, in addition, by with applying 1 same method of example, Make electroconductive adhesive sheet.
(embodiment 11)
The thickness of conductive adhesive oxidant layer is changed to 15 μm by 9 μm, in addition, by with applying 1 same method of example, Make electroconductive adhesive sheet.
(embodiment 12)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (1B), and by conductive adhesive The thickness of oxidant layer is changed to 18 μm by 9 μm, in addition, by with applying 1 same method of example, making electroconductive adhesive sheet.
(embodiment 13)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (1B), and by conductive adhesive The thickness of oxidant layer is changed to 13 μm by 9 μm, in addition, by with applying 1 same method of example, making electroconductive adhesive sheet.
(embodiment 14)
Plating non-woven fabrics A is replaced using plating non-woven fabrics E, in addition, embodiment 14 is made similarly to Example 1 Electroconductive adhesive sheet.
(embodiment 15)
Conductive substrate (A) is replaced using conductive substrate (F), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(embodiment 16)
Conductive substrate (A) is replaced using conductive substrate (G), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(embodiment 17)
Conductive substrate (A) is replaced using conductive substrate (H), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(comparative example 1)
Conductive substrate (A) is replaced using conductive substrate (I), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(comparative example 2)
Conductive substrate (A) is replaced using conductive substrate (J), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(comparative example 3)
Conductive substrate (A) is replaced using conductive substrate (K), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(comparative example 4)
Conductive substrate (A) is replaced using conductive substrate (L), in addition, by with applying 1 same method of example, making Make electroconductive adhesive sheet.
(comparative example 5)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (1A-4), in addition, are led to It crosses and applies 1 same method of example, make electroconductive adhesive sheet.
(comparative example 6)
Conductive adhesive compositions (1A-1) are replaced using conductive adhesive compositions (1A-5), in addition, are led to It crosses and applies 1 same method of example, make electroconductive adhesive sheet.
(reference example 1)
Use 9 μm of the electrolytic copper foil (CF-T9FZ-SV, the FUKUDA METAL's paper tinsel powder that are handled through inorganic antirust (chromate) of thickness Industrial group's system) conductive substrate (A) is replaced, in addition, by with applying 1 same method of example, making electroconductive adhesive sheet.
Above-mentioned conductive substrate, conductive adhesive oxidant layer and electroconductive adhesive sheet are conducted the following evaluation, by what is obtained The results are shown in following tables.Wherein, acrylic acid amount in table represents acrylic acid compared with being used in the manufacture of acrylic acid series copolymer The usage amount (quality %) of the total amount of monomer component.In addition, the metal powder amount in table represents electroconductive particle compared with electric conductivity The whole content (quality %) of adhesive phase.In addition, by the tracing ability evaluation result of embodiment 1 and reference example 1 be shown in Fig. 3 and Fig. 4.
[grain size]
The grain size of electroconductive particle refers to, uses the laser diffraction formula particle size distribution of Shimadzu Scisakusho Ltd Device SALD-3000, the value that decentralized medium is measured using isopropanol.
[electric conductivity (electroconductive adhesive sheet)]
By the brass electrode for being pasted on 25mm × 25mm on one side of the electroconductive adhesive sheet of 30mm width × 30mm width. The copper foil (35 μm of thickness) of 30mm × 80mm is pasted in the another side of electroconductive adhesive sheet.
In the state of the load for applying face pressure 20N from the upper surface of above-mentioned brass electrode, in above-mentioned brass electrode With connection terminal on above-mentioned copper foil, in the environment of 23 DEG C, 50%RH, flowed through using milliohm table (NF circuit design systems) measure The resistance value during electric current of 10 μ A.Using the situation that above-mentioned resistance value is below 500m Ω as qualification.
[thickness (conductive adhesive oxidant layer)]
It is made to each conductive adhesive compositions is used to form 25 μm of conductive adhesive oxidant layer backing on stripping film The sample that PET film (You Niji can company system S25) forms, uses the thickness gauge " TH- of TESTER SANGYO CO .LTD. 102 " measure its thickness.The value that the thickness that above-mentioned stripping film and PET film are subtracted from said determination value is obtained is glued as electric conductivity The thickness of mixture layer.
[thickness (electroconductive adhesive sheet)]
The thickness of electroconductive adhesive sheet is measured using the thickness gauge " TH-102 " of TESTER SANGYO CO .LTD..
[electric conductivity (conductive substrate)]
The conductive substrate of 30mm width × 30mm width is clamped with the brass electrode of two 25mm × 25mm, from In a state that the upper surface of brass electrode applies the load of face pressure 20N, the connection terminal on each brass electrode, 23 DEG C, In the environment of 50%RH, resistance value when flowing through the electric current of 10 μ A is measured using milliohm table (NF circuits design system).
[bonding force]
Prepare the electroconductive adhesive sheet of 20mm width, the polyethylene terephthalate film of 25 μm of thickness is used in one side (Unitika Corp S25) carries out backing, as test film.
Next, in the environment of 23 DEG C, 50%RH, hair grinding (ヘ ア have been carried out using the water-proof abrasive paper of No. 360 ラ イ Application is ground) adhesive phase of above-mentioned test film is pasted on the stainless steel plate (hereinafter referred to as stainless steel plate) of processing, make 2.0kg Roller surface round trip on it, so that they are crimped.
Next, by the above-mentioned material through crimping place at normal temperatures 1 it is small when after, use tension testing machine (TENSILON RTA-100, A＆D Co., Ltd. system), it is tested with tensile speed 300mm/min, is removed so as to measure 180 degree at normal temperatures Bonding force.The experiment of above-mentioned bonding force is carried out to each adhesive phase (adhesive phase on two sides) of electroconductive adhesive sheet, it will be relatively low Value be recorded in table.
[tracing ability]
Electroconductive adhesive sheet is pasted onto depth 5mm with hand, the of roughly semicircular of width 10mm has differential metal On plate, for evaluating differential tracing ability.
○：It can follow differential.
×：It can not follow differential, float or rupture.
[re-workability 1]
Glue residua is whether there is on stainless steel during to measuring bonding force by the above method to evaluate.
◎：Without glue residua.
○：There is glue residua in scope of the area compared with stainless steel plate less than 10%.
×：There is glue residua in the scope that the area compared with stainless steel plate is more than 10%.
[re-workability 2]
It evaluates whether electroconductive adhesive sheet ruptures when measuring bonding force by the above method.Use 5 conductions Property bonding sheet implement experiment, evaluated by following benchmark.
◎：5 do not rupture.
○：4 do not rupture.
×：2 or more rupture.
[table 1]
[table 2]
[table 3]
By above table as it can be seen that the bonding sheet tracing ability of the embodiment 1~18 of the present application is excellent and cementability, conduction Property, re-workability are also good.Although and the bonding sheet tracing ability of comparative example 1~4, electric conductivity, excellent in adhesion, re-workability It is apparent poor.The bonding sheet poorly conductive of comparative example 5.Adhering adhesive sheet, the re-workability of comparative example 6 are poor.In addition, reference example Bonding sheet tracing ability is poor, floats and ruptures in differential portion.
Symbol description
1 conductive substrate
2 conductive adhesive oxidant layer

Claims (13)

1. a kind of electroconductive adhesive sheet, which is characterized in that
It is the electroconductive adhesive sheet in the conductive adhesive phase of at least one side of conductive substrate,
The conductive substrate be to wet type Polyester non-woven fabrics base material implementation include electroless plating plating and It obtaining, the thickness of the wet type Polyester non-woven fabrics base material is 5~50 μm,
Whole compared with the conductive adhesive oxidant layer, the conductive adhesive oxidant layer contains leading for the mass % of 3 mass %~50 Conductive particles, the adhesive ingredients of the conductive adhesive layer is acrylic adhesive composition.
2. electroconductive adhesive sheet according to claim 1, the electroconductive particle contains copper or nickel.
3. electroconductive adhesive sheet according to claim 1, the electroless plating is using at least 1 in copper or nickel The processing that kind carries out.
4. electroconductive adhesive sheet according to claim 1, the conductive substrate is by wet type Polyester nonwoven Cloth base material is implemented further to implement after electroless plating obtained from electroless plating or electrolytic coating processing.
5. electroconductive adhesive sheet according to claim 4,
The conductive substrate is by further real after electroless plating Copper treatment is implemented to wet type Polyester non-woven fabrics base material Apply electrolytic ni plating processing obtained from.
6. electroconductive adhesive sheet according to claim 4, the conductive substrate is by wet type Polyester non-woven fabrics Base material is implemented successively obtained from electroless plating Copper treatment, electrolytic copper plating processing and electrolytic ni plating processing.
7. electroconductive adhesive sheet according to claim 1,
The conductive adhesive oxidant layer is to use the acrylic adhesive shape containing electroconductive particle and acrylic acid series polymeric compounds Into layer, the acrylic acid series polymeric compounds be by make containing 1 mass % the polymerizing monomer components of the acrylic acid of~6 mass % and It obtains.
8. electroconductive adhesive sheet according to claim 1, the weight per unit area of the wet type Polyester non-woven fabrics base material For 2g/m2~20g/m2。
9. electroconductive adhesive sheet according to claim 1, the tension in the MD directions of the wet type Polyester non-woven fabrics base material Intensity is 2N/20mm~30N/20mm, and the tensile strength in its TD direction is 0.3N/20mm~30N/20mm.
10. electroconductive adhesive sheet according to claim 1, the thickness of the conductive adhesive oxidant layer is 3 μm~25 μm, and The average grain diameter d50 of the electroconductive particle is 3 μm~20 μm.
11. electroconductive adhesive sheet according to claim 1, the conductive adhesive oxidant layer and the conductive substrate pass through It is stacked with 40 DEG C~120 DEG C of temperature heat lamination.
12. the manufacturing method of the electroconductive adhesive sheet any one of a kind of claim 1~11, which is characterized in that institute At least one side for stating conductive substrate is placed with the material of the conductive adhesive oxidant layer with 40 DEG C~120 DEG C of temperature progress layer Pressure.
13. a kind of electric terminal, be pasted on component with the electroconductive adhesive sheet any one of claim 1~11 and Into structure.
CN201480021189.0A 2013-04-19 2014-04-10 Electroconductive adhesive sheet, its manufacturing method and use its electric terminal Active CN105164223B (en)

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